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About half of the lunar meteorites in our collections are feldspathic breccias. Acquiring geochronologic information from these breccias is challenging due to their low radioactive‐element contents and their often polymict nature. We used high‐spatial‐resolution (5 μm) NanoSIMS (nanoscale secondary ion mass spectrometry) U‐Pb dating technique to date micro‐zircons in the lunar feldspathic meteorites Dhofar 1528 and Dhofar 1627. Three NanoSIMS dating spots of two zircon grains from Dhofar 1528 show a discordia with an upper intercept at 4354 ± 76 Ma and a lower intercept at 332 ± 1407 Ma (2σ, MSWD = 0.01, p = 0.91). Three spots of two zircon grains in Dhofar 1627 define a discordia with an upper intercept at 3948 ± 30 Ma and a lower intercept at 691 ± 831 Ma (2σ, MSWD = 0.40, p = 0.53). Both samples likely experienced shock metamorphism caused by impacts. Based on the clastic nature, lack of recrystallization and the consistent U‐Pb and Pb‐Pb dates of the zircons in Dhofar 1528, the U‐Pb date of 4354 Ma is interpreted as the crystallization age of its Mg‐suite igneous precursor. Some of the Dhofar 1627 zircons show poikilitic texture, a crystallization from the matrix impact melt, so the U‐Pb date of 3948 Ma corresponds to an impact event, likely the Imbrium basin‐forming event. These data are the first radiometric ages for these two meteorites and demonstrate that in situ (high spatial resolution) U‐Pb dating has potential for extracting geochronological information about igneous activities and impact events from lunar feldspathic and polymict breccias. [ABSTRACT FROM AUTHOR]

As the earliest-dated solids in our Solar System, calcium-aluminum-rich inclusions (CAIs) provide a record of their formation environment near the young Sun and hold clues to the formation of planetary-scale isotopic reservoirs in the solar protoplanetary disk. Although CAIs from several CV, CK, CM, CO, and ordinary chondrites have been analyzed previously for their Ti isotopic compositions, CAIs from just three CV chondrites have been analyzed for their Cr isotopic compositions, and only a handful of CAIs have been measured for both their Ti and Cr isotopic compositions. We report mass-independent Ti and Cr isotopic anomalies in several CAIs from CV and CK chondrites; this is the first report of the Cr isotopic composition of a CAI from a CK chondrite. With these additional data, we aim to better constrain the compositional range of CAIs in ε50Ti versus ε54Cr space, thereby facilitating the isotopic characterization of the material inherited by the solar protoplanetary disk and the role of CAIs in the formation of distinct planetary-scale isotopic reservoirs in our early Solar System. The narrow range in isotopic anomalies in CAIs when compared to other early-formed refractory inclusions such as platy hibonite crystals (PLACs) and spinel-hibonite inclusions (SHIBs) suggests that CAIs record the mixing of these precursor materials and the averaging of their larger isotopic anomalies. The isotopic composition of CAIs is therefore likely the result of a combination of factors, including mixing of material inherited from their formation region, heterogeneous carrier phase distribution, and thermal processing in the disk. The ε50Ti and ε54Cr isotopic compositions of CAIs are not correlated, further demonstrating that these isotopic anomalies have different carrier phases. The Ti and Cr isotopic compositions of CAIs additionally show that CAIs alone cannot be responsible for the compositional difference between the non-carbonaceous chondritic (NC) and carbonaceous chondritic (CC) isotopic reservoirs but nevertheless do play a role in the formation of these large-scale isotopic reservoirs in the early Solar System. [ABSTRACT FROM AUTHOR]

Calcium-aluminum-rich inclusions (CAIs) and chondrules are among the most predominant chondritic components contained within primitive meteorites. As CAIs are the first solids to form in the solar nebula, they contain a record of its earliest chemical and physical processes. Here we combine electron backscatter diffraction (EBSD) and 26Al-26Mg chronology techniques to determine the crystallographic properties and ages of CAI components that provide temporal as well as spatial constraints on their origins and subsequent processing in the solar protoplanetary disk. We find evidence of shock deformation within a CAI, suggesting that it was deformed as a free-floating object soon after the CAI formation at the beginning of the Solar System. Our results suggest that even though CAIs and chondrules formed in distinct environments and on different timescales, they were likely affected by similar shock processes that operated over large temporal (0 to ∼4 Ma) and spatial (0.2 to at least 2 to 3 au) extents. Our results imply that nebular shock events were active on a wider scale in the solar protoplanetary disk than previously recognized. [ABSTRACT FROM AUTHOR]

Abstract: New high-precision W isotope measurements are presented for 33 iron meteorites from 8 magmatic groups (IC, IIAB, IID, IIIAB, IIIE, IIIF, I VA and IVB), 2 non-magmatic groups (IAB–IIICD and IIE), and one ungrouped iron (Deep Springs). All magmatic irons have ε 182W values that are, within errors, equal to, or less radiogenic than, the Solar System initial of −3.47±0.20. A method was developed to correct the measured ε 182W values of magmatic iron meteorites for the presence of cosmogenic effects produced during space exposure to galactic cosmic rays. The corrected data provide new constraints on the timing of metal-silicate differentiation in iron meteorite parent bodies, which must have taken place within a few million years (<2 to 6 My) of condensation of calcium–aluminum-rich inclusions (CAIs). Metal-silicate differentiation ages (from 182Hf–182W systematics) were combined with parent body sizes (from metallographic cooling rates) into a model of planetesimal heating by 26Al-decay, to constrain the accretion timescale of iron meteorite parent bodies. Accretion of iron meteorite parent bodies most likely occurred within 1.5 My of the formation of CAIs. The fast accretion times of iron meteorite parent bodies are consistent with dynamical models indicating that these objects may have originated in the terrestrial planet-forming region, where the accretion rates were high. Our W isotopic data for non-magmatic IAB–IIICD and IIE irons provide new constraints for their formation mechanisms. In particular, they support formation of IAB–IIICD iron meteorites by melting during a single collision event dated at 4–7 My after formation of the Solar System. [Copyright &y& Elsevier]

Archean rocks may provide a record of early Earth environments. However, such rocks have often been metamorphosed by high pressure and temperature, which can overprint the signatures of their original formation. Here, we show that the early Archean banded rocks from Isua, Akilia, and Innersuartuut, Greenland, are enriched in heavy iron isotopes by 0.1 to 0.5 per mil per atomic mass unit relative to igneous rocks worldwide. The observed enrichments are compatible with the transport, oxidation, and subsequent precipitation of ferrous iron emanating from hydrothermal vents and thus suggest that the original rocks were banded iron formations (BIFs). These variations therefore support a sedimentary origin for the Akilia banded rocks, which represent one of the oldest known occurrences of water-laid deposits on Earth. [ABSTRACT FROM AUTHOR]

Iron isotopes record the physical parameters, such as temperature and redox conditions, during differentiation processes on rocky bodies. Here we report the results of a correlated investigation of iron isotope compositions and silicon contents of silicon-bearing metal grains from several aubritic meteorites. Based on their Fe isotopic and elemental Si compositions and thermal modelling, we show that these aubrite metals equilibrated with silicates at temperatures ranging from ~ 1430 to ~ 1640 K and likely sampled different depths within their asteroidal parent body. The highest temperature in this range corresponds to their equilibration at a minimum depth of up to ~ 35 km from the surface of the aubrite parent body, followed by brecciation and excavation by impacts within the first ~ 4 Myr of Solar System history. [ABSTRACT FROM AUTHOR]

A close relationship between CM and CO chondrites has been suggested by previous petrologic and isotopic studies, leading to the suggestion that they may originate from similar precursor materials or even a common parent body. In this study, we evaluate the genetic relationship between CM and CO chondrites using Ti, Cr, and O isotopes. We first provide additional constraints on the ranges of ε50Ti and ε54Cr values of bulk CM and CO chondrites by reporting the isotopic compositions of CM2 chondrites Murchison, Murray, and Aguas Zarcas and the CO3.8 chondrite Isna. We then report the ε50Ti and ε54Cr values for several ungrouped and anomalous carbonaceous chondrites that have been previously reported to exhibit similarities to the CM and/or CO chondrite groups, including Elephant Moraine (EET) 83226, EET 83355, Grosvenor Mountains (GRO) 95566, MacAlpine Hills (MAC) 87300, MAC 87301, MAC 88107, and Northwest Africa (NWA) 5958, and the O-isotope compositions of a subset of these samples. We additionally report the Ti, Cr, and O isotopic compositions of additional ungrouped chondrites LaPaz Ice Field (LAP) 04757, LAP 04773, Lewis Cliff (LEW) 85332, and Coolidge to assess their potential relationships with known carbonaceous and ordinary chondrite groups. LAP 04757 and LAP 04773 exhibit isotopic compositions indicating they are low-FeO ordinary chondrites. The isotopic compositions of Murchison, Murray, Aguas Zarcas, and Isna extend the compositional ranges defined by the CM and CO chondrites in ε50Ti versus ε54Cr space. The majority of the ungrouped carbonaceous chondrites with documented similarities to the CM and/or CO chondrites plot outside the CM and CO group fields in plots of ε50Ti versus ε54Cr, Δ17O versus ε50Ti, and Δ17O versus ε54Cr. Therefore, based on differences in their Ti, Cr, and O isotopic compositions, we conclude that the CM, CO, and ungrouped carbonaceous chondrites likely represent samples of multiple distinct parent bodies. We also infer that these parent bodies formed from precursor materials that shared similar isotopic compositions, which may indicate formation in regions of the protoplanetary disk that were in close proximity to each other. [ABSTRACT FROM AUTHOR]

Calcium-aluminum-rich inclusions (CAIs) are the first solids to form in the early Solar System, and they exhibit nucleosynthetic anomalies in many isotope systems. The overwhelming majority of isotopic data for CAIs is limited to inclusions from the CV chondrite Allende and a few other CV, CO, CM, and ordinary chondrites. It is therefore important to ascertain whether previously reported values for CAIs are representative of the broader CAI-forming region and to make a more rigorous assessment of the extent and implications of isotopic heterogeneity in the early Solar System. Here, we report the mass-independent Ti isotopic compositions of a suite of 23 CAIs of diverse petrologic and geochemical types, including 11 from Allende and 12 from 7 other CV3 and CK3 chondrites; the data for CAIs from CK chondrites are the first reported measurements of Ti isotopic compositions of CAIs from this meteorite class. The resolved variation in the mass-independent Ti isotopic compositions of these CAIs indicates that the CAI-forming region of the early Solar System preserved isotopic variability. Nevertheless, the range of Ti isotopic compositions reported here for CAIs from CV and CK chondrites falls within the range observed in previously analyzed CAIs from CV, CO, CM, and ordinary chondrites. This implies that CAIs from CV, CK, CO, CM, and ordinary chondrites originated from a common nebular source reservoir characterized by mass-independent isotopic variability in Ti (and certain other elements). We further interpret these data to indicate that the Ti isotopic anomalies in CAIs represent the isotopic signatures of supernova components in presolar grains that were incorporated into the Solar System in an initially poorly mixed reservoir that was progressively homogenized over time. We conclude that the differing degrees of isotopic variability observed for different elements in normal CAIs are the result of distinct carrier phases and that these CAIs were likely formed towards the final stages of homogenization of the large-scale isotopic heterogeneity that initially existed in the solar nebula. [ABSTRACT FROM AUTHOR]

Calcium-aluminum-rich inclusions (CAIs) are the oldest dated materials that provide crucial information about the isotopic reservoirs present in the early Solar System. For a variety of elements, CAIs have isotope compositions that are uniform yet distinct from later formed solid material. However, despite being the most abundant metal in the Solar System, the isotopic composition of Fe in CAIs is not well constrained. In an attempt to determine the Fe isotopic compositions of CAIs, we combine extensive work from a previously studied CAI sample set with new isotopic work characterizing mass-dependent and mass-independent (nucleosynthetic) signatures in Mg, Ca, and Fe. This investigation includes work on three mineral separates of the Allende CAI Egg 2. For all isotope systems investigated, we find that in general, fine-grained CAIs exhibit light mass-dependent isotopic signatures relative to terrestrial standards, whereas igneous CAIs have heavier isotopic compositions relative to the fine-grained CAIs. Importantly, the mass-dependent Fe isotope signatures of bulk CAIs show a range of both light (fine-grained CAIs) and heavy (igneous CAIs) isotopic signatures relative to bulk chondrites, suggesting that Fe isotope signatures in CAIs largely derive from mass fractionation events such as condensation and evaporation occurring in the nebula. Such signatures show that a significant portion of the secondary alteration experienced by CAIs, particularly prevalent in fine-grained inclusions, occurred in the nebula prior to accretion into their respective parent bodies. Regarding nucleosynthetic Fe isotope signatures, we do not observe any variation outside of analytical uncertainty in bulk CAIs compared to terrestrial standards. In contrast, all three Egg 2 mineral separates display resolved mass-independent excesses in 56Fe compared to terrestrial standards. Furthermore, we find that the combined mass-dependent and nucleosynthetic Fe isotopic compositions of the Egg 2 mineral separates are well correlated, likely indicating that Fe indigenous to the CAI is mixed with less anomalous Fe, presumably from the solar nebula. Thus, these reported nucleosynthetic anomalies may point in the direction of the original Fe isotope composition of the CAI-forming region, but they likely only provide a minimum isotopic difference between the original mass-independent Fe isotopic composition of CAIs and that of later formed solids. [ABSTRACT FROM AUTHOR]

Although there is limited direct evidence for supernova input into the nascent Solar System, many models suggest it formed by the gravitational collapse of a molecular cloud that was triggered by a nearby supernova. Existing lines of evidence, mostly in the form of short-lived radionuclides present in the early Solar System, are potentially consistent with this hypothesis, but still allow for alternative explanations. Since the natural production of 126 Sn is thought to occur only in supernovae and this isotope has a short half-life ( 126 Sn→ 126 Te, t 1/2 = 235 ky), the discovery of extant 126 Sn would provide unequivocal proof of supernova input to the early Solar System. Previous attempts to quantify the initial abundance of 126 Sn by examining Sn-Te systematics in early solids have been hampered by difficulties in precisely measuring Te isotope ratios in these materials. Thus, here we describe a novel technique that uses hydride generation to dramatically increase the ionization efficiency of Te—an approximately 30-fold increase over previous work. This introduction system, when coupled to a MC-ICPMS, enables high-precision Te isotopic analyses on samples with <10 ng of Te. We used this technique to analyze Te from a unique set of calcium-aluminum-rich inclusions (CAIs) that exhibit an exceptionally large range in Sn/Te ratios, facilitating the search for the short-lived isotope 126 Sn. This sample set shows no evidence of live 126 Sn, implying at most minor input of supernova material during the time at which the CAIs formed. However, based on the petrology of this sample set combined with the higher than expected concentrations of Sn and Te, as well as the lack of nucleosynthetic anomalies in other isotopes of Te suggest that the bulk of the Sn and Te recovered from these particular refractory inclusions is not of primary origin and thus does not represent a primary signature of Sn-Te systematics of the protosolar nebula during condensation of CAIs or their precursors. Although no evidence of supernova input was found based on Sn-Te systematics in this sample set, hydride generation represents a powerful tool that can now be used to further explore Te isotope systematics in less altered materials. [ABSTRACT FROM AUTHOR]

We present the results of laboratory experiments in which a forsterite-rich melt estimated to be a potential precursor of Allende CMS-1 FUN CAI was evaporated into vacuum for different lengths of time at 1900 °C. The evaporation of this melt resulted in residues that define trajectories in chemical as well as magnesium, silicon and oxygen isotopic composition space and come very close to the measured properties of CMS-1. The isotopic composition of the evaporation residues was also used to determine the kinetic isotopic fractionation factors [ α 2,1 (vapor-melt) defined as the ratio of isotopes 2 and 1 of a given element in the evaporating gas divided by their ratio in the evaporating source] for evaporation of magnesium ( α 25,24 for 25 Mg/ 24 Mg), silicon ( α 29,28 for 29 Si/ 28 Si) and oxygen ( α 18,16 for 18 O/ 16 O) from the forsterite-rich melt at 1900 °C. The values of α 25,24 = 0.98383 ± 0.00033 and α 29,28 = 0.99010 ± 0.00038 are essentially independent of change in the melt composition as evaporation proceeds. In contrast, α 18,16 changes from 0.9815 ± 0.0016 to ∼0.9911 when the residual melt composition changes from forsteritic to melilitic. Using the determined values of α 25,24 and α 29,28 and present-day bulk chemical composition of the CMS-1, the composition of the precursor of the inclusion was estimated to be close to the clinopyroxene + spinel + forsterite assemblage condensed from a solar composition gas. The correspondence between the chemical composition and isotopic fractionation of experimental evaporation residues and the present-day bulk chemical and isotopic compositions of CMS-1 is evidence that evaporation played a major role in the chemical evolution of CMS-1. [ABSTRACT FROM AUTHOR]

A procedure was developed to accurately measure the W isotopic compositions of iron meteorites with a precision of better than ±0.1 ϵ On ϵ182W and ϵ184W (normalized to 186W/183W) Purification of W was achieved through a two step, ion-exchange procedure. In most cases, the yield is better than 80%, and purified W solutions are clear of matrix elements and direct isobars of W. The final W solutions were analyzed using a Micromass Isoprobe multicollector inductively coupled plasma mass spectrometer (MC-ICPMS). Tests performed on mixtures of terrestrial standards and meteorite samples demonstrate that the method is accurate and that ϵ182W variations as small as ∼0.1 ϵ can be detected. Analyses of three different aliquots of the Gibeon (P/A) iron meteorite obtained over a period of 6 months show identical ϵ182W values with a weighted mean of 3.38 ± 0.05, consistent with literature data for NA iron meteorites, and indicating that the metal-silicate differentiation event in its parent body was either contemporaneous with or slightly postdated (by up to ∼2.5 My) the formation of refractory inclusions. We demonstrate our ability to measure ϵ184W accurately and precisely (within ±0.1 ϵ), which is useful for characterizing cosmogenic and nucleosynthetic effects that may be present in iron meteorites. We also report for the first time measurements of ϵ180W, albeit with large error bars (<±4 ϵ, in most cases). [ABSTRACT FROM AUTHOR]

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The performance of multi-collector secondary ion mass spectrometry (MC-SIMS) for Mg isotope ratio analysis was evaluated using 17 olivine and 5 pyroxene reference materials (RMs). The Mg isotope composition of these RMs was accurately and precisely determined by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), and these measured isotope ratios were used to evaluate SIMS instrumental mass bias as a function of the forsterite (Fo) content of olivine. The magnitude of the Mg isotope matrix effects were ~3‰ in δ25Mg, and are a complex function of olivine Fo content, that ranged from Fo 59.3 to Fo 100. In addition to these Mg isotope matrix effects, Si+ ion yields and Mg+/Si+ ion ratios varied as a complex function of the Fo content of the olivine RMs. For example, Si+ ion yields varied by ~33%. Based on the observations, we propose instrumental bias correction procedures for SIMS Mg isotope analysis of olivine using a combination of Mg+/Si+ ratios and Fo content of olivine. Using this correction method, the accuracy of δ25Mg analyses is 0.3‰, except for analysis of olivine with Fo 86 – 88 where instrumental biases and Mg+/Si+ ratios change dramatically with Fo content, making it more difficult to assess the accuracy of Mg isotope ratio measurements by SIMS over this narrow range of Fo content. Five pyroxene RMs (3 orthopyroxenes and 2 clinopyroxenes) show smaller ranges of instrumental bias (~1.4‰ in δ25Mg) as compared to the olivine RMs. The instrumental bias for the 3 orthopyroxene RMs do not define a linear relationship with respect to enstatite (En) content, that ranged from En 8 5. 5 – 96.3. The clinopyroxene RMs have similar En and wollastonite (Wo) contents but have δ25Mg values that differ by 0.5‰ relative to their δ25Mg values determined by MC-ICP-MS. These results indicate that additional factors (e.g., minor element abundances) likely contribute to SIMS instrumental mass fractionation. In order to better correct for these SIMS matrix effects, additional pyroxene RMs with various chemical compositions and known Mg isotope ratios are needed. • We investigated matrix effects of SIMS Mg isotope analyses of olivine and pyroxene. • Instrumental bias of olivine is estimated by using numbers of olivine standards. • Matrix effect depends on both forsterite content and Mg+/Si+ secondary ion yields. • Precision and accuracy of Mg isotope analysis of olivine is improved to be ≤0.3‰. • Radio-frequency plasma ion source has an advantage on precise Mg isotope analyses. [ABSTRACT FROM AUTHOR]

The isotopic compositions of samples returned from Cb-type asteroid Ryugu and Ivuna-type (CI) chondrites are distinct from other carbonaceous chondrites, which has led to the suggestion that Ryugu/CI chondrites formed in a different region of the accretion disk, possibly around the orbits of Uranus and Neptune. We show that, like for Fe, Ryugu and CI chondrites also have indistinguishable Ni isotope anomalies, which differ from those of other carbonaceous chondrites. We propose that this unique Fe and Ni isotopic composition reflects different accretion efficiencies of small FeNi metal grains among the carbonaceous chondrite parent bodies. The CI chondrites incorporated these grains more efficiently, possibly because they formed at the end of the disk's lifetime, when planetesimal formation was also triggered by photoevaporation of the disk. Isotopic variations among carbonaceous chondrites may thus reflect fractionation of distinct dust components from a common reservoir, implying CI chondrites/Ryugu may have formed in the same region of the accretion disk as other carbonaceous chondrites.

Characterization of the elemental distribution of samples with rough surfaces has been strongly desired for the analysis of various natural and artificial materials. Particularly for pristine and rare analytes with micrometer sizes embedded on specimen surfaces, non-invasive and matrix effect-free analysis is required without surface polishing treatment. To satisfy these requirements, we proposed a new method employing the sequential combination of two imaging modalities, i.e., microenergy-dispersive X-ray fluorescence (micro-XRF) and Raman micro-spectroscopy. The applicability of the developed method is tested by the quantitative analysis of cation composition in micrometer-sized carbonate grains on the surfaces of intact particles sampled directly from the asteroid Ryugu. The first step of micro-XRF imaging enabled a quick search for the sparsely scattered and micrometer-sized carbonates by the codistributions of Ca 2+ and Mn 2+ on the Mg 2+ - and Fe 2+ -rich phyllosilicate matrix. The following step of Raman micro-spectroscopy probed the carbonate grains and analyzed their cation composition (Ca 2+ , Mg 2+ , and Fe 2+ + Mn 2+ ) in a matrix effect-free manner via the systematic Raman shifts of the lattice modes. The carbonates were basically assigned to ferroan dolomite bearing a considerable amount of Fe 2+ + Mn 2+ at around 10 atom %. These results are in good accordance with the assignments reported by scanning electron microscopy-energy-dispersive X-ray spectroscopy, where the thin-sectioned and surface-polished Ryugu particles were applicable. The proposed method requires neither sectioning nor surface polishing; hence, it can be applied to the remote sensing apparatus on spacecrafts and planetary rovers. Furthermore, the non-invasive and matrix effect-free characterization will provide a reliable analytical tool for quantitative analysis of the elemental distribution on the samples with surface roughness and chemical heterogeneity at a micrometer scale, such as art paintings, traditional crafts with decorated shapes, as well as sands and rocks with complex morphologies in nature.

The sample tubes on board NASA's Perseverance rover are designed to contain rocks, regolith, and atmospheric gases and are hermetically sealed on the surface of Mars to minimize sample loss, alteration, and contamination. Following a robust testing program during mission development, it was determined that the helium (He) leak rates of flight-like sample tubes sealed under a range of conditions were typically no greater than ∼10 -10 standard cubic centimeters per second (scc/s); leak rates below this value could not be measured since this is the detection limit of commercially available He leak detectors. This limit was adequate to meet mission requirements. However, some scientific objectives could be compromised by sample tube leak rates even below 10 -10 scc/s, thus motivating a more sensitive technique for establishing leak rates. This study investigated He leak rates on six flight-like sample tubes using a static mode mass spectrometer. Room temperature He leak rates of the six sample tubes ranged from ∼8.8 × 10 -17 to ∼4.6 × 10 -14 scc/s. One sample tube was analyzed at eight different temperatures, ranging from -51°C to +42°C, and yielded He leak rates correlated with temperature that varied from ∼1.7 × 10 -15 to ∼1.4 × 10 -13 scc/s, respectively. Our results confirm and extend previous findings demonstrating that the Mars 2020 sample tube seals are likely to be very leak-tight, with leak rates <10 -13 scc/s. These leak rates are sufficiently low that the impact of gas egress or ingress is expected to be negligible.

Studies of material returned from Cb asteroid Ryugu have revealed considerable mineralogical and chemical heterogeneity, stemming primarily from brecciation and aqueous alteration. Isotopic anomalies could have also been affected by delivery of exogenous clasts and aqueous mobilization of soluble elements. Here, we show that isotopic anomalies for mildly soluble Cr are highly variable in Ryugu and CI chondrites, whereas those of Ti are relatively uniform. This variation in Cr isotope ratios is most likely due to physicochemical fractionation between 54 Cr-rich presolar nanoparticles and Cr-bearing secondary minerals at the millimeter-scale in the bulk samples, likely due to extensive aqueous alteration in their parent bodies that occurred [Formula: see text] after Solar System birth. In contrast, Ti isotopes were marginally affected by this process. Our results show that isotopic heterogeneities in asteroids are not all nebular or accretionary in nature but can also reflect element redistribution by water.

Preliminary analyses of asteroid Ryugu samples show kinship to aqueously altered CI (Ivuna-type) chondrites, suggesting similar origins. We report identification of C-rich, particularly primitive clasts in Ryugu samples that contain preserved presolar silicate grains and exceptional abundances of presolar SiC and isotopically anomalous organic matter. The high presolar silicate abundance (104 ppm) indicates that the clast escaped extensive alteration. The 5 to 10 times higher abundances of presolar SiC (~235 ppm), N-rich organic matter, organics with N isotopic anomalies (1.2%), and organics with C isotopic anomalies (0.2%) in the primitive clasts compared to bulk Ryugu suggest that the clasts formed in a unique part of the protoplanetary disk enriched in presolar materials. These clasts likely represent previously unsampled outer solar system material that accreted onto Ryugu after aqueous alteration ceased, consistent with Ryugu's rubble pile origin.

Carbonaceous meteorites are thought to be fragments of C-type (carbonaceous) asteroids. Samples of the C-type asteroid (162173) Ryugu were retrieved by the Hayabusa2 spacecraft. We measured the mineralogy and bulk chemical and isotopic compositions of Ryugu samples. The samples are mainly composed of materials similar to those of carbonaceous chondrite meteorites, particularly the CI (Ivuna-type) group. The samples consist predominantly of minerals formed in aqueous fluid on a parent planetesimal. The primary minerals were altered by fluids at a temperature of 37° ± 10°C, about [Formula: see text] million (statistical) or [Formula: see text] million (systematic) years after the formation of the first solids in the Solar System. After aqueous alteration, the Ryugu samples were likely never heated above ~100°C. The samples have a chemical composition that more closely resembles that of the Sun's photosphere than other natural samples do.

The extraterrestrial materials returned from asteroid (162173) Ryugu consist predominantly of low-temperature aqueously formed secondary minerals and are chemically and mineralogically similar to CI (Ivuna-type) carbonaceous chondrites. Here, we show that high-temperature anhydrous primary minerals in Ryugu and CI chondrites exhibit a bimodal distribution of oxygen isotopic compositions: 16 O-rich (associated with refractory inclusions) and 16 O-poor (associated with chondrules). Both the 16 O-rich and 16 O-poor minerals probably formed in the inner solar protoplanetary disk and were subsequently transported outward. The abundance ratios of the 16 O-rich to 16 O-poor minerals in Ryugu and CI chondrites are higher than in other carbonaceous chondrite groups but are similar to that of comet 81P/Wild2, suggesting that Ryugu and CI chondrites accreted in the outer Solar System closer to the accretion region of comets.

Little is known about the origin of the spectral diversity of asteroids and what it says about conditions in the protoplanetary disk. Here, we show that samples returned from Cb-type asteroid Ryugu have Fe isotopic anomalies indistinguishable from Ivuna-type (CI) chondrites, which are distinct from all other carbonaceous chondrites. Iron isotopes, therefore, demonstrate that Ryugu and CI chondrites formed in a reservoir that was different from the source regions of other carbonaceous asteroids. Growth and migration of the giant planets destabilized nearby planetesimals and ejected some inward to be implanted into the Main Belt. In this framework, most carbonaceous chondrites may have originated from regions around the birthplaces of Jupiter and Saturn, while the distinct isotopic composition of CI chondrites and Ryugu may reflect their formation further away in the disk, owing their presence in the inner Solar System to excitation by Uranus and Neptune.

Samples returned from Mars would be placed under quarantine at a Sample Receiving Facility (SRF) until they are considered safe to release to other laboratories for further study. The process of determining whether samples are safe for release, which may involve detailed analysis and/or sterilization, is expected to take several months. However, the process of breaking the sample tube seal and extracting the headspace gas will perturb local equilibrium conditions between gas and rock and set in motion irreversible processes that proceed as a function of time. Unless these time-sensitive processes are understood, planned for, and/or monitored during the quarantine period, scientific information expected from further analysis may be lost forever. At least four processes underpin the time-sensitivity of Mars returned sample science: (1) degradation of organic material of potential biological origin, (2) modification of sample headspace gas composition, (3) mineral-volatile exchange, and (4) oxidation/reduction of redox-sensitive materials. Available constraints on the timescales associated with these processes supports the conclusion that an SRF must have the capability to characterize attributes such as sample tube headspace gas composition, organic material of potential biological origin, as well as volatiles and their solid-phase hosts. Because most time-sensitive investigations are also sensitive to sterilization, these must be completed inside the SRF and on timescales of several months or less. To that end, we detail recommendations for how sample preparation and analysis could complete these investigations as efficiently as possible within an SRF. Finally, because constraints on characteristic timescales that define time-sensitivity for some processes are uncertain, future work should focus on: (1) quantifying the timescales of volatile exchange for core material physically and mineralogically similar to samples expected to be returned from Mars, and (2) identifying and developing stabilization or temporary storage strategies that mitigate volatile exchange until analysis can be completed. Executive Summary Any samples returned from Mars would be placed under quarantine at a Sample Receiving Facility (SRF) until it can be determined that they are safe to release to other laboratories for further study. The process of determining whether samples are safe for release, which may involve detailed analysis and/or sterilization, is expected to take several months. However, the process of breaking the sample tube seal and extracting the headspace gas would perturb local equilibrium conditions between gas and rock and set in motion irreversible processes that proceed as a function of time. Unless these processes are understood, planned for, and/or monitored during the quarantine period, scientific information expected from further analysis may be lost forever . Specialist members of the Mars Sample Return Planning Group Phase 2 (MSPG-2), referred to here as the Time-Sensitive Focus Group, have identified four processes that underpin the time-sensitivity of Mars returned sample science: (1) degradation of organic material of potential biological origin, (2) modification of sample headspace gas composition, (3) mineral-volatile exchange, and (4) oxidation/reduction of redox-sensitive materials (Figure 2). Consideration of the timescales and the degree to which these processes jeopardize scientific investigations of returned samples supports the conclusion that an SRF must have the capability to characterize: (1) sample tube headspace gas composition, (2) organic material of potential biological origin, (3) volatiles bound to or within minerals, and (4) minerals or other solids that host volatiles (Table 4). Most of the investigations classified as time-sensitive in this report are also sensitive to sterilization by either heat treatment and/or gamma irradiation (Velbel et al., 2022). Therefore, these investigations must be completed inside biocontainment and on timescales that minimize the irrecoverable loss of scientific information (i.e., several months or less; Section 5) . To that end, the Time-Sensitive Focus Group has outlined a number of specific recommendations for sample preparation and instrumentation in order to complete these investigations as efficiently as possible within an SRF (Table 5). Constraints on the characteristic timescales that define time-sensitivity for different processes can range from relatively coarse to uncertain (Section 4). Thus, future work should focus on: (1) quantifying the timescales of volatile exchange for variably lithified core material physically and mineralogically similar to samples expected to be returned from Mars, and (2) identifying and developing stabilization strategies or temporary storage strategies that mitigate volatile exchange until analysis can be completed. List of Findings FINDING T-1: Aqueous phases, and oxidants liberated by exposure of the sample to aqueous phases, mediate and accelerate the degradation of critically important but sensitive organic compounds such as DNA. FINDING T-2: Warming samples increases reaction rates and destroys compounds making biological studies much more time-sensitive. MAJOR FINDING T-3: Given the potential for rapid degradation of biomolecules, (especially in the presence of aqueous phases and/or reactive O-containing compounds) Sample Safety Assessment Protocol (SSAP) and parallel biological analysis are time sensitive and must be carried out as soon as possible. FINDING T-4: If molecules or whole cells from either extant or extinct organisms have persisted under present-day martian conditions in the samples, then it follows that preserving sample aliquots under those same conditions ( i.e., 6 mbar total pressure in a dominantly CO 2 atmosphere and at an average temperature of -80 ° C) in a small isolation chamber is likely to allow for their continued persistence. FINDING T-5: Volatile compounds ( e.g., HCN and formaldehyde) have been lost from Solar System materials stored under standard curation conditions. FINDING T-6: Reactive O-containing species have been identified in situ at the martian surface and so may be present in rock or regolith samples returned from Mars. These species rapidly degrade organic molecules and react more rapidly as temperature and humidity increase. FINDING T-7: Because the sample tubes would not be closed with perfect seals and because, after arrival on Earth, there will be a large pressure gradient across that seal such that the probability of contamination of the tube interiors by terrestrial gases increases with time, the as-received sample tubes are considered a poor choice for long-term gas sample storage. This is an important element of time sensitivity. MAJOR FINDING T-8: To determine how volatiles may have been exchanged with headspace gas during transit to Earth, the composition of martian atmosphere (in a separately sealed reservoir and/or extracted from the witness tubes), sample headspace gas composition, temperature/time history of the samples, and mineral composition (including mineral-bound volatiles) must all be quantified. When the sample tube seal is breached, mineral-bound volatile loss to the curation atmosphere jeopardizes robust determination of volatile exchange history between mineral and headspace. FINDING T-9: Previous experiments with mineral powders show that sulfate minerals are susceptible to H 2 O loss over timescales of hours to days. In addition to volatile loss, these processes are accompanied by mineralogical transformation. Thus, investigations targeting these minerals should be considered time-sensitive. FINDING T-10: Sulfate minerals may be stabilized by storage under fixed relative-humidity conditions, but only if the identity of the sulfate phase(s) is known a priori . In addition, other methods such as freezing may also stabilize these minerals against volatile loss. FINDING T-11: Hydrous perchlorate salts are likely to undergo phase transitions and volatile exchange with ambient surroundings in hours to days under temperature and relative humidity ranges typical of laboratory environments. However, the exact timescale over which these processes occur is likely a function of grain size, lithification, and/or cementation. FINDING T-12: Nanocrystalline or X-ray amorphous materials are typically stabilized by high proportions of surface adsorbed H 2 O. Because this surface adsorbed H 2 O is weakly bound compared to bulk materials, nanocrystalline materials are likely to undergo irreversible ripening reactions in response to volatile loss, which in turn results in decreases in specific surface area and increases in crystallinity. These reactions are expected to occur over the timescale of weeks to months under curation conditions. Therefore, the crystallinity and specific surface area of nanocrystalline materials should be characterized and monitored within a few months of opening the sample tubes. These are considered time-sensitive measurements that must be made as soon as possible. FINDING T-13: Volcanic and impact glasses, as well as opal-CT, are metastable in air and susceptible to alteration and volatile exchange with other solid phases and ambient headspace. However, available constraints indicate that these reactions are expected to proceed slowly under typical laboratory conditions ( i.e., several years) and so analyses targeting these materials are not considered time sensitive. FINDING T-14: Surface adsorbed and interlayer-bound H 2 O in clay minerals is susceptible to exchange with ambient surroundings at timescales of hours to days, although the timescale may be modified depending on the degree of lithification or cementation. Even though structural properties of clay minerals remain unaffected during this process (with the exception of the interlayer spacing), investigations targeting H 2 O or other volatiles bound on or within clay minerals should be considered time sensitive upon opening the sample tube. FINDING T-15: Hydrated Mg-carbonates are susceptible to volatile loss and recrystallization and transformation over timespans of months or longer, though this timescale may be modified by the degree of lithification and cementation. Investigations targeting hydrated carbonate minerals (either the volatiles they host or their bulk mineralogical properties) should be considered time sensitive upon opening the sample tube. MAJOR FINDING T-16: Current understanding of mineral-volatile exchange rates and processes is largely derived from monomineralic experiments and systems with high surface area; lithified sedimentary rocks (accounting for some, but not all, of the samples in the cache) will behave differently in this regard and are likely to be associated with longer time constants controlled in part by grain boundary diffusion. Although insufficient information is available to quantify this at the present time, the timescale of mineral-volatile exchange in lithified samples is likely to overlap with the sample processing and curation workflow ( i.e., 1-10 months; Table 4). This underscores the need to prioritize measurements targeting mineral-hosted volatiles within biocontainment. FINDING T-17: The liberation of reactive O-species through sample treatment or processing involving H 2 O ( e.g., rinsing, solvent extraction, particle size separation in aqueous solution, or other chemical extraction or preparation protocols) is likely to result in oxidation of some component of redox-sensitive materials in a matter of hours. The presence of reactive O-species should be examined before sample processing steps that seek to preserve or target redox-sensitive minerals. Electron paramagnetic resonance spectroscopy (EPR) is one example of an effective analytical method capable of detecting and characterizing the presence of reactive O-species. FINDING T-18: Environments that maintain anoxia under inert gas containing <<1 ppm O 2 are likely to stabilize redox-sensitive minerals over timescales of several years. MAJOR FINDING T-19: MSR investigations targeting organic macromolecular or cellular material, mineral-bound volatile compounds, redox sensitive minerals, and/or hydrous carbonate minerals can become compromised at the timescale of weeks (after opening the sample tube), and scientific information may be completely lost within a time timescale of a few months. Because current considerations indicate that completion of SSAP, sample sterilization, and distribution to investigator laboratories cannot be completed in this time, these investigations must be completed within the Sample Receiving Facility as soon as possible.

Stable isotope ratios of H, C, and O are powerful indicators of a wide variety of planetary geophysical processes, and for Mars they reveal the record of loss of its atmosphere and subsequent interactions with its surface such as carbonate formation. We report in situ measurements of the isotopic ratios of D/H and (18)O/(16)O in water and (13)C/(12)C, (18)O/(16)O, (17)O/(16)O, and (13)C(18)O/(12)C(16)O in carbon dioxide, made in the martian atmosphere at Gale Crater from the Curiosity rover using the Sample Analysis at Mars (SAM)'s tunable laser spectrometer (TLS). Comparison between our measurements in the modern atmosphere and those of martian meteorites such as ALH 84001 implies that the martian reservoirs of CO2 and H2O were largely established ~4 billion years ago, but that atmospheric loss or surface interaction may be still ongoing.